silver nanoparticles: an eco-friendly approach for ... · (sathishkumar et al., 2009) and ocimum...

International Journal of Scientific Research in Environmental Sciences, 3(2), pp. 0047-0061, 2015

Available online at http://www.ijsrpub.com/ijsres

ISSN: 2322-4983; ©2015; Author(s) retain the copyright of this article

http://dx.doi.org/10.12983/ijsres-2015-p0047-0061

47

Mini Review Paper

Silver Nanoparticles: An Eco-Friendly Approach for Mosquito Control

Amita Hajra, Naba Kumar Mondal*

Environmental Chemistry Laboratory, Department of Environmental Science, The University of Burdwan, Burdwan, 713104,

India

*Corresponding author: [email protected], Cell: 09434545694

Received 20 October 2014; Accepted 23 January 2015

Abstract. Size of silver nanoparticles ranges from 1 to 100 nm. The unique properties of silver nanoparticles (AgNP) help in

molecular diagnostics, several types of treatments and research purposes. The major methods used for silver nanoparticle

synthesis are the physical and chemical methods. Silver nanoparticles can be produced by both physical and chemical methods.

To overcome the problems faced by the huge expenses of physical and chemical methods and toxic substances absorbed onto

them, biological method to synthesize AgNP is a suitable alternative. Silver nanoparticles have been used potentially to control

larval stages of mosquitoes in the experimental conditions. Perhaps due to insertion of nanoparticles in cutical layer of larvae.

Successful application of this may occur in near future to check mosquito borne diseases. The various modes of synthesis and

application along with successive progress are discussed in this paper. The main focus of this review paper on effective and

efficient synthesis of silver nanoparticles from bio-origin and exploring their various prospective applications towards

mosquito larvicidal activity. Moreover, it also vividly described about the bio-molecules which directly reduced silver ions and

probable mechanism of AgNPs interaction with mosquito larvae.

Keywords: Silver nanoparticles, Green methods, Bio-molecules, Capping agent, Mosquito larvicidal activity

1. INTRODUCTION

Easily available mosquito ides in the market are

synthetic chemicals. If we constantly apply these

costly chemicals it has many detrimental effects on

non-target organism including human, harm

ecological balance. Moreover, when used for a

prolonged time, it may produce resistance strain of

mosquito (Anayaele and Amusan, 2003). In areas of

medicine, catalysis, water treatment, solar energy

conversion technological and environmental problems

may be solved by nanomaterials. Silver nanoparticles

(AgNPs) can be synthesized by chemicals such as

Sodium borohydride for reduction of monovalent

silver atom to zerovalent silver atom (Solomon et al.,

2007). To oxidize methanol to formaldehyde and

ethylene to ethylene oxide silver is used as catalyst

widely. Colloidal silver having good conductivity,

catalytic and antibacterial ability, being chemically

stable is a catalyst of choice (Sharma et al., 2009). In

China, in elevators of railway station, silver

nanoparticles are used as microbial agent. In surgery

silver nanoparticles are used as anti microbials as

AgNPs reduce infection by its anti-inflammmatory,

anti-permeability and anti angiogenic properties

(Sahayaraj and Rajesh, 2011). The silver nanoparticles

capped with polymetaacrylic acid (PMA) and

produced by UV irradiation was previously

synthesized and used for sensing application. The

biocompatibility and harmlessness of the PMA

polymer make it appropriate to be employed in

biomedical application. Sap-Iam et al. (2010) used

PMA-capped silver nanoparticles synthesized by

photoreduction by UV-irradiation that was very

effective for larvicidal activity towards Aedes aegypti.

In physical and chemical methods high pressure,

energy, temperature and toxic substances (Lok et al.,

2007). Where as in biological synthesis of AgNP, the

reduction of Ag+ ions of AgNO3 to AgNPs is done by

plant biomolecules. So, green synthesis of AgNP is

more advanced than chemical and physical methods

because green syntheses of AgNPs are cost effective

and environment friendly. In several literatures, it is

reported that plants that are used to synthesize silver

nanoparticles contains proteins, alkaloids, flavonoids,

triterpenes, lectins etc. Proteins present in leaves

extract probably reduces silver to silver nanoparticles.

The exact mechanisms of formation of silver

nanoparticles still need to be studied. It is clear that

proteins, carbohydrates and polyphenols are involved

in AgNP synthesis (Marimuthu et al., 2001). Shankar

et al. (2004) suggested the role of protein and

mailto:[email protected]

Hajra and Mondal


48

terpenoids from Azadirachta indica (Neem) leaf broth

has tremendous effect for synthesis of AgNPs. On the

other hand, Loo et al. (2012) report ed that Allicin and

other carbohydrates from Allium sativum (garlic)

extract) were shown to be active compounds

catalyzing AgNPs synthesis.

This review provides an idea of the bio-origin

AgNPs and their applicability on mosquito larvicidal

activity. However, this work also highlighted the bio-

chemical agent present in plants or trees and their

potentiality to acts as capping agent which established

the synthesized AgNPs.

2. MATERIALS AND METHODS

Preparation of plant extract:

To prepare the plant extract plant materials are

washed thoroughly and air dried for two days .then the

plant parts are powdered using electric grinder.10 gm.

of that powder is boiled with 100 ml of distilled water

for 10 minutes. The extract is filtered and kept in

refrigerator. The extract is used within 7 days. Then

metal salt is dissolved in 100 ml of double distilled

water will be used as the stock solution.

2.1. Synthesis of silver nanoparticles

The plant extract was mixed with metal solution at

different ratio (1:1, 1:3, 1:5, and 1:9) (Mondal et al.,

2014; Medda et al., 2014). It was incubated until a

reddish brown colour; appeared (Priyadarshini et al.,

2012). The biosynthesis reaction started within few

minutes and the colour reaction was observed in

which clear AgNO3 solution turned into brown colour

which indicates that formation of silver nanoparticles

(Fig. 1) (Swamy et al., 2014).

This colour difference was due to the reduction of

silver ions (Sinha et al., 2014). Metallic nanoparticles

scatter and absorb light at certain wave lengths due to

the resonant collective excitations of charge density at

the interface between a conductor and an insulator,

phenomena known as surface plasmon resonances

(Sinha et al. 2014). The optical response of silver

nanoparticles can be regulated by various factors such

as particle size, shape and environment, providing a

starting point for emerging research fields such as

surface plasmon-based photonics or plasma nics

(Noguez et al., 2007).

Fig. 1: Colour change during the bioreduction of AgNO3 into AgNPs Using plant extract: (A) before synthesis, (B) after

synthesis

2.2. Green synthesis of silver nanoparticles by

previous workers

As science and industry is developing to more

advancement, green chemistry and its processes are

integrating more progressively because there is a

global effort to reduce generated hazardous waste.

Recently green silver nanoparticles have been

synthesized using various plants like Pongamia

pinnata (Raut et al., 2010), Nelumbo nucifera

(Santhoshkumar et al., 2010), Cinnamon zeylanicum

(Sathishkumar et al., 2009) and Ocimum sanctum

(Ahmed et al., 2010). Silver nanoparticles synthesized

using leaf extract of False Daisy plant (Eclipta

prostrate) have larvicidal activity against Anopheles

and Culex mosquitoes (Rajakumar and Rahuman,

2011). In their study, slow reduction of the aqueous

silver ions along with the shape-directing effects of


49

the constituents of the E.prostrata extract play a key

role in the formation of the silver nanocircular in

shape with smooth edges nanoparticles. However,

many research papers recently highlighted for

synthesis of silver nanoparticles from terrestrial and

aquatic plant extracts.

2.3. Characterization of silver nanoparticles

The solution with nanoparticles is characterized by

Scanning Electron Micrograph (SEM) and X-Ray

Diffraction (XRD) (Fig. 2). Nanoparticle solutions are

dried in a Petridish. Then the dried powder is

collected and taken to be sputter coated with gold

before being mounted on aluminium stubs. The

specimens are viewed and photographed using a 15 kv

scanning electron microscope. Infrared photograph is

recorded by Fourier Transform Infrared Spectroscopy

(FTIR) is carried out using a BRUKER (Tensor 27).

FTIR spectrophotometer is connected to a photo

acustic cell in the spectral range from 4000 to 400 cm-

1. Absorbance of the nanoparticles is measured by

UV-Vis spectrophotometer and Fluorescent

spectrophotometer. The production of nanoparticles

synthesized from aquous extracts of plant parts is

evaluated through UV-Vis spectrophotometer in a

range of wavelength from 300 to 600 nm (Fig.3).The

peak indicates the production of nanoparticle.

Fig. 2: (A) SEM image and (B) EDX profile (Adopted from Roopan et al., 2013)

Fig. 3: UV-vis absorption spectra of silver nanoparticles synthesized from leaf extracts of plant species.

2.4. Mosquito rearing and collection

Larvae of Culex quinquefasciatus and Anopheles

subpictus were collected from stagnant water and rice

fields. Subsequently the larvae were identified from

various authentic institutes. Mosquito larvae were

reared in plastic and enamel trays containing

dechlorinated tap water. Several generations of

mosquitoes were maintained in the laboratory

(Kamaraj et al., 2009).

2.5. Determination of the larvicidal activity of

Silver nanoparticles:

For each test, 25 late third instar of mosquito larvae

was kept in different beakers containing 249 ml of

dechlorinated water. Nanoparticles were added to the

Hajra and Mondal


50

beakers at different concentration. For each

concentration five replicates were performed. Each

test included a set of control groups. Larval mortality

was recorded after 24 h of exposure. The lethal

concentrations were calculated by probit analysis

(Veerakumar et al., 2013).

3. RESULTS AND DISCUSSIONS

3.1. Mechanism of formation of silver

nanoparticles

Since the early early 1900s, it was well known that

plant extracts are able to reduce metal ions but the

reducing agent and its nature was not well understood.

But the previous literature anticipated that the

biomolecules such as polyphenols can be responsible

for reduction of silver ion and synthesis of silver

nanoparticles. The mechanisms which give

antioxidant properties to other molecules promote the

reduction of silver ions to atoms. The OH groups

present in polyphenol molecules abstructs hydrogen

which is the main mechanism (Sivaraman et al.,

2009). However, McDonald et al. (1996) and Yoosaf

et al.(2007) reported in their research paper that tannic

acid which has 25 phenolic –OH groups in its

structure , but only 10 pairs of O-dihydoxy phenyl

groups are capable of taking part in the redox reaction

to form quinines (Fig.4) and donate electrons, because

of the chelating action of adjacent hydroxyl groups.

The released electron can be used up for reduction of

silver ion to metallic silver.

Fig. 4: Oxidation of phenolic groups to ketones

Although other plant origin compounds such as

Glutathione, Geraniol, Epicatechin, L-lysine etc.

reduce silver ion to zero valent silver. The enzyme

NADPH-dependent dehydrogenase plays some role in

the reduction process of Ag+ to AgNP (Mukherjee et

al., 2008). In which route the electrons are shuttled is

still not known and needs more research. Which

component or environment is responsible for high

stability of nanoparticles is unknown.

On the other hand, Kesharalani et al. (2009),

highlighted the synthesis of stable silver nanoparticles

by using leaf extract of Datura metel. They also

reported the presence of alkaloids, enzymes, proteins,

alcoholic compounds and polysaccharides in leaf

extract of Datura metel which reduces siver ions to

zero valent silver nanoparticle. They also demanded

that quinol and chlorophyll pigments present in the

extracts were also responsible for reduction of Ag+

ions and stabilization of Ag nanoparticles. The

possible chemical constituents (Fig. 5) which are

present in the biomolecules can directly take part in

the synthesis of silver nanoparticles (Dubey et al.,

2009; Huang et al., 2007). Another study conducted

by Prabhu and Poulose, (2012) has resolved that the

main mechanisms behind the plant assisted

nanoparticles are phytochemicals. Phytochemicals

such as terpenoids, ketones, flavones, amides,

aldehydes, carboxylic acids, quinines, organic acids

and flavones are water-soluble and immediately

reduce of the ions. Emodin, an anthraquinone

undergoes tautomerization can be found in

xerophytes, forms silver nanoparticles. In the

mesophytes, three types of benzoquinones can be

found, cyperoquinone, dietchequinone, and remirin.

Jha et al. (2009) suggested that phytochemicals

directly reduces the ions and forms silver

nanoparticles

.


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Fig. 5: Possible chemical constituents of plant extract responsible for the bioreduction of metal ions (Dubey et al., 2009;

Huang et al., 2007).

So far mortality of mosquito larvae is concerned, it

has been found that LC50 as low as 0.56 mg/l ranges to

606.5 mg/l (Table 3).The mosquito species Aedes

aegypti showed very sensitivity towards the mortality

with a plant species Cadaba indica followed by

Euphorbia hirta (LC50 0.585 mg/l),Alstonia

macrophylla (LC50 1.82 mg/l),Pedilanthus

tithymaloides(LC50 1.461 mg/l) and Nelumbo nucifera

(LC50 4.44 mg/l) and highest LC50 was recorded for

Murraya koenigii. Anopheles stephensi and Culex

quinquifasciatus showed 50% mortality in much

higher concentration compared to Aedes aegypti. The

LC50 of Anopheles stephensi ranges from 1.74 mg/l

(for Plumeria rubra) to 18.40 mg/l (Feronia

elephantum). Whereas LC50 of Culex

quinquifasciatus ranges from 1.10 mg/l (Nelumbo

nucifera) to 130.30 mg/l (Sida acuta). Moreover,

Table 3 also demonstrated that the lowest LC90 of

Aedes aegypti, Anopheles stephensi and Culex

quinquifasciatus are 0.891 mg/l (Euphorbia

hirta),4.23 mg/l (Plumeria rubra) and 3.59 mg/l

(Nelumbo nucifera) respectively. On the other hand,

very limited researchers reported about Anopheles

subpictus which showed minimum values of LC50 and

LC90 are 2.15mg/l (Nerium oleander) and 68.41 mg/l

(Nerium oleander) respectively. Present review based

on the bio-origin chemical constituents for the

synthesis of AgNPs and all the mentioned

plant/tree/macrophytes are presented in Fig.6.

3.2. Interaction effect of nanoparticle with

mosquito larvae

Bannoth et al. (2014) proposed the cause of larval

death which is due to the mechanism that

nanoparticles in the intracellular space bind to

proteins containing sulphur or phosphorus containing

compounds (DNA). This leads to enzyme and

organelle degradation. Cell death is mainly caused by

decreased membrane permeability and disturbed

proton motive force which leads to cellular function

loss. However, High larvicidal activity of AgNPs can

be attributed with their lower particle size. Moreover,

smaller particle size increase surface area to volume

ratio and thus increases its action against larvae

(Borase et al., 2013). Sosenkova and Egorova give

similar results of effect of particle size and shape on

antibacterial application (Sosenkova and Egorova,

2011).

Hajra and Mondal


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Table 1: Biosynthesis of silver nanoparticles using plant extracts. Plant Metal Size and Shape References

Acalypha indica Ag 20–30 nm; spherical Krishnaraj et al. (2010)

Allium sativum(garlic clove) Ag 4–22 nm; spherical Ahamed et al. (2011)

Aloe vera Ag 50–350 nm; spherical,

triangular

Chandran et al. (2006)

Boswellia ovalifoliolata Ag 30–40 nm Ankanna et al. (2010)

Calotropis procera Ag 150–1000 nm Babu and Prabu (2011)

Camelia sinensis Ag 30–40 nm Vilchis-Nestor et al. (2008)

Carica papaya Ag 25–50 nm Jain et al. (2009)

Catharanthus roseus Ag 48–67 nm Kannan et al. (2011)

Ponarulselvam et al. (2012)

Chenopodium album Ag 10–30 nm ; quasi-spherical

shape

Dwivedi and Gopal (2010)

Cinnamomum camphora Ag 55–80 nm Huang et al. (2007)

Cinnamomum camphora Ag 3.2–20 nm; cubic hexagonal

crystalline

Yang et al. (2010)

Citrus sinensis peel Ag 10±1 nm ;spherical Kaviya et al. (2011)

Coleus amboinicus Lour Ag 8±0.8 nm Subramanian (2012)

Coleus aromaticus Ag 44 nm Vanaja et al. (2010)

Curcuma longa Ag 31-40 nm, spherical Sathishkumar et al. (2010)

Datura metel Ag 16–40 nm; quasilinear

superstructures

Kesharwani et al. (2009)

Desmodium triflorum Ag 5–20 nm Ahmad et al. (2010)

Eclipta prostrate Ag 10–20 nm Ankamwar et al. (2005)

Dioscorea bulbifera Ag 35–60 nm, triangles,

pentagons, hexagons

Rajakumar and Rahuman

(2011)

Emblica officinalis Ag 10–20 nm Ankamwar et al. (2005)

Eucalyptus hybrid Ag 50–150 nm Dubey et al. (2009)

Garcinia

mangostana(mangosteen leaf)

Ag 35 nm Veerasamy et al. (2010)

Gelidiella acerosa Ag 22 nm Vivek et al. (2011)

Memecylon edule Ag 20–50 nm, triangular,

circular, hexagonal

Elavazhagan and

Arunachalam (2011)

Melia azedarach Ag 78 nm, Spherical Sukirtha et al. (2011)

Mentha piperita (peppermint) Ag Spherical Ali et al. (2011); Parashar et

al. (2009)

Moringa oleifera Ag 57 nm Prasad and Elumalai (2011)

Mucuna pruriens Ag 6–17.7 nm, spherical Arulkumar and Sabesan

(2010)

Musa paradisiacal Ag 20 nm Bankar et al. (2010)

Nelumbo nucifera(lotus) Ag 25–80 nm, spherical,

triangular

Santhoshkumar et al. (2011)

Rhododedendron dauricam Ag 25–40 nm; spherical Mittal et al. (2012)

Rosa rugosa Ag 30–60 nm Dubey et al. (2010a)

Sesuvium portulacastrum Ag 5–20 nm; spherical Nabikhan et al. (2010)

Swietenia mahogani

(mahogany)

Ag 20 nm Mondal et al. (2011)

Syzygium cumini Ag 29–92; spherical Banerjee (2011); Kumar et al.

(2010)

Tanacetum vulgare (tansy

fruit)

Ag 16 nm Dubey et al. (2010b)

Trachyspermum copticum Ag 6–50 nm Vijayaraghavan et al. (2012)


53

Table 2: Application towards larvicidal activity Plant species Mosquito species Mortality rate Reference

Euphorbia hirta Anopheles stephensi

LC50 -27.89 ppm

LC90 -69.94 ppm

Priyadarshini et al. 2012.

Rhizophora mucronata

Aedes aegypti

Anopheles stephensi

LC50-0.585 mg/l

LC90-0.891 mg/l

LC50-2.615 mg/l

LC90-6.29 mg/l

Gnanadesigan et al. 2011

Cocos nucifera

Anopheles stephensi

Culex quinquifasciatus

LC50-87.24 mg/l

LC90-230.90 mg/l

LC50-49.89 mg/l

LC90-84.85 mg/l

Roopan et al. 2013

Sida acuta

Anopheles stephensi

Aedes aegypti


LC50-109.94 µg/ml

LC90-202.42 µg/ml

LC50-119.32 µg/ml

LC90-213.84 µg/ml

LC50-130.30 µg/ml

LC90-228.20 µg/ml

Veerakumar et al. 2013

Cadaba indica

Anopheles stephensi


LC50-15.41 mg/l

LC90-61.07 mg/l

LC50-15.44 mg/l

LC90-58.37 mg/l

Kalimuthu et al. 2013

Annona squamosa

Aedes aegypti

Anopheles stephensi

LC50-0.56 ppm

LC50-2.12 ppm

Arjunan et al. 2012

Murraya koenigii

Anopheles stephensi

Aedes aegypti

LC50-536.11 ppm

LC90-1187.62 ppm

LC50-606.5 ppm

LC90-1273.06 ppm

Suganya et al. 2013

Tinospora cordifolia

Anopheles subpictus


LC50-6.34 mg/l

LC50-6.96 mg/l

Jayaseelan et al. 2011

Nerium oleander

Anopheles subpictus

LC50-33.99 ppm

LC90-68.41 ppm

Roni et al. 2013

Nelumbo nucifera

Anopheles subpictus


LC50-0.69 mg/l

LC90-2.15 mg/l

LC50-1.10 mg/l

LC90-3.59 mg/l

Santhoshkumar et al. 2011

Jatropha gossypifolia

Aedes aegypti

Anopheles stephensi

LC50-4.44 mg/l

LC90-9.52 mg/l

LC50-4.90 mg/l

LC90-12.60 mg/l

Boarse et al. 2013

Euphorbia tirucalli

Aedes aegypti

Anopheles stephensi

LC50-6.75 mg/l

LC90-15.96 mg/l

LC50-8.18 mg/l

LC90-15.76 mg/l

Boarse et al. 2013

Hajra and Mondal


54

Pedilanthus tithymaloides

Aedes aegypti

Anopheles stephensi

LC50-6.75 mg/l

LC90-15.96 mg/l

LC50-6.46 mg/l

LC90-14.94 mg/l

Boarse et al. 2013

Alstonia macrophylla

Aedes aegypti

Anopheles stephensi

LC50-8.74 mg/l

LC90-15.94 mg/l

LC50-9.55 mg/l

LC90-17.41 mg/l

Boarse et al. 2013

Plumeria rubra

Aedes aegypti

Anopheles stephensi

LC50-1.82 ppm

LC90-4.32 ppm

LC50-1.74 ppm

LC90-4.23 ppm

Patil et al. 2012

Feronia elephantum

Anopheles stephensi

Aedes aegypti


LC50-11.56 µg/ml

LC90-20.56 µg/ml

LC50-13.13 µg/ml

LC90-23.12 µg/ml

LC50-14.19 µg/ml

LC90-24.30 µg/ml

Veerakumar et al. 2014a

Heliotropium indicum

Anopheles stephensi

Aedes aegypti


LC50-18.40 µg/ml

LC90-32.45 µg/ml

LC50-20.10 µg/ml

LC90-35.97 µg/ml

LC50-21.84 µg/ml

LC90-38.10 µg/ml

Veerakumar et al. 2014b

Pedilanthus tithymaloides Aedes aegypti

LC50-1.461 mg/l

Sundaravadivelan et al.2013

Eclipta prostrata


Anopheles subpictus

LC50-4.56 mg/l

LC90-13.14 mg/l

LC50-5.14 mg/l

LC90-25.68 mg/l

Rajakumar and Rahuman.

2011

Pergularia daemia Aedes aegypti

Anopheles stephensi

LC50-6.18 mg/l

LC90-12.95 mg/l

LC50-6.47 mg/l

LC90-14.08 mg/l

Patil et al. 2012

Vinca rosea Anopheles stephensi


LC50-16.84 mg/ml

LC90-68.62 mg/ml

LC50-43.80 mg/ml

LC90-120.54 mg/ml

Subarani et at. 2013

Hibiscus rosasinenesis Aedes albopictus

100% mortality at 5.0 mg/l

conc.

Sareen et al. 2012

Drypetes roxburghii Culex quinquifasciatus

Anopheles stephensi

100% mortality at 10 ppm

88 % mortality at 5 ppm



Halder et al. 2013


55

Hajra and Mondal


56

Hibiscus rosasinensis Drypetes roxburghii

Fig. 6: The plant species from where AgNPs has been synthesized by previous researchers.

5. CONCLUSION

If plant extracts are used to make nanoparticles it will

be of low cost, environment friendly and easily scaled

up. Plant induced synthesis of nanoparticles is most

suitable method because it does not leave any toxic

contaminants. In health industry, storage of food,

textile industry and many other environmental field,

AgNPs has been used as an anti-bacterial agent. The

evidence of toxicity of AgNP is still not well

established although it has been widely used for

decades. Therefore, future research should be focused

on the toxicity of silver nanoparticles on both aquatic

animals and teristeral plants.

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Mrs Amita Hajra presently is working as research fellow in the department of Environmental

Science, The University of Burdwan. Mrs Hajra completed her masters degree from Zoology

department of the same University. Her special interest is on synthesis of silver nanoparticles

and its application on larvicidal activity of mosquito.

Dr Naba Kumar Mondal presently holding the position as Assistant professor in the

department of Environmental Science, The University of Burdwan, India. Dr Mondal has

experience more than 16 years of teaching and research in both Education and

Environmental Science (masters degree). His research interest includes: Pure

Science:Adsorption Chemistry, Nutrient dynamics, indoor pollution, soil Chemistry, Plant

Physiology, Social Science: corporal punishment, development of teaching methodology,

noise and its impact on school children etc. Dr Mondal also published more than 130

research papers in reputed International and National Journals and four (04) Ph.D. scholars

(upto May’ 2014) and has been serving as an guest Editor and reviewer in many prestigious

International Journals.

silver nanoparticles: an eco-friendly approach for ... · (sathishkumar et al., 2009) and ocimum...

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